Phosphors with narrow green emission

ABSTRACT

Green emitting phosphors have the empirical composition RE 1−w A w M x E y , where RE may be one or more Rare Earth elements (for example, Eu or Gd), A may be one or more elements selected from the group Mg, Ca, Sr, or Ba, M may be one or more elements selected from the group Al, Ga, B, In, Sc, Lu or Y, E may be one or more elements selected from the group S, Se, O, or Te, w is greater than or equal to zero, or greater than or equal to 0.01, or greater than or equal to 0.05, and less than or equal to about 0.8, 2≤x≤4, and 4≤y≤7.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims benefit of priority to U.S. Provisional Patent Application No. 62/673,044 titled “Phosphors With Narrow Green Emission” and filed May 17, 2018, which is incorporated herein by reference in its entirety.

This invention was made with federal government support from the National Science Foundation under award number 1534771. The federal government has certain rights in the invention. This invention was also made with an award from the Kentucky Cabinet for Economic Development, Office of Entrepreneurship, under Grant Agreement KSTC-184-512-17-247 with the Kentucky Science and Technology Corporation.

FIELD OF THE INVENTION

The invention relates generally to phosphors having narrow green emission.

BACKGROUND

Alkaline earth thiogallate and alkaline earth thioaluminate phosphors activated with europium are known in the art for both electroluminescent systems and phosphor converted LED systems. These materials can readily absorb the emission from blue, violet, or near UV emitting light sources such as the commonplace InGaN light emitting diodes. These typically green phosphor materials can be used independently to generate a green light, or they can be combined with other phosphor materials to generate white or other colored light. Similarly, these green phosphor materials may be combined, for example, with a blue or other LED and a red phosphor in order to generate the backlighting unit for a display, such as a mobile phone, tablet, laptop, monitor, or television.

In general lighting, it is often desirable to have a broad emission spectrum to improve the color rendering index (R_(a)) or other quality of light metrics, such as CQS or TM-30-15. However, sometimes in lighting it is desirable to provide extra light in certain wavelength regions in order to accentuate certain features; for instance, grocery store display cases for beef may include extra light in the red region of the spectrum, similarly, spinach or green peppers may appear more pleasing when the lighting provides extra light in certain green wavelengths.

In display backlighting, it is more desirable to have a narrow emission wavelength so that the color (a) appears more saturated and widens the green vertex of the color gamut, and (b) sustains fewer losses when passing through the green filter of a typical LCD filter system, because the majority of its intensity is well aligned with the highest transmissivity of the filter.

SUMMARY

Phosphors of the present invention address the challenge of helping to preferentially saturate certain green regions of the emission spectrum for lighting applications and improve the green gamut point of a display backlight unit by providing a phosphor composition with a relatively narrow green emission spectrum.

In one aspect of the invention, green emitting phosphors have the empirical composition RE_(1−w)A_(w)M_(x)E_(y), where RE may be one or more Rare Earth elements (for example, Eu or Gd), A may be one or more elements selected from the group Mg, Ca, Sr, or Ba, M may be one or more elements selected from the group Al, Ga, B, In, Sc, Lu or Y, E may be one or more elements selected from the group S, Se, O, or Te, w is greater than or equal to zero, or greater than or equal to 0.01, or greater than or equal to 0.05, w is less than or equal to about 0.8, 2≤x≤4, and 4≤y≤7. In some variations, w is greater than or equal to about 0.30 and less than or equal to about 0.66.

In another aspect of the invention, a phosphor converted LED comprises such a green emitting phosphor.

These and other embodiments, features and advantages of the present invention will become more apparent to those skilled in the art when taken with reference to the following more detailed description of the invention in conjunction with the accompanying drawings that are first briefly described.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows emission spectra for phosphor examples 1, 2, 3, 5 and 8 and for an internal reference standard.

FIG. 2 shows excitation spectra for phosphor examples 1, 2, 3, 5 and 8.

FIG. 3 shows emission spectra for examples 22-28 and for an internal reference standard.

FIG. 4 shows emission spectra for examples 29-37.

FIG. 5 shows excitation spectra for examples 29-36.

FIG. 6A and FIG. 6B show, respectively, x-ray powder diffraction profiles for examples 29-32 and examples 33-36.

FIG. 7 shows X-ray powder diffraction profiles for example 47 after second and third firings.

FIG. 8 shows X-ray powder diffraction profiles for example 51 after second and third firings.

FIG. 9 emission spectra for examples 47-51 after a second firing.

FIG. 10 shows excitation spectra for examples 47-51 after a second firing.

FIG. 11 shows emission spectra for examples 47-51 after a third firing.

FIG. 12 shows excitation spectra for examples 47-51 after a third firing.

FIG. 13 shows emission spectra for examples 52 and 53.

FIG. 14 shows the emission spectra for examples 54 to 57.

FIG. 15 shows the emission spectrum for example 59.

FIG. 16 shows excitation spectra for examples 54 to 57.

FIG. 17 shows X-ray powder diffraction profiles for examples 54 to 57.

FIG. 18 shows the emission spectrum for example phosphor-converted LED 1.

FIG. 19 shows the emission spectrum for example phosphor-converted LED 2.

FIG. 20 shows the emission spectrum for example phosphor-converted LED 3.

FIG. 21 shows the emission spectrum for example phosphor-converted LED 4.

FIG. 22 shows the emission spectrum for example phosphor-converted LED 5.

FIG. 23 shows the emission spectrum for example phosphor-converted LED 6.

DETAILED DESCRIPTION

The following detailed description should be read with reference to the drawings, which depict selective embodiments and are not intended to limit the scope of the invention. The detailed description illustrates by way of example, not by way of limitation, the principles of the invention. This description will clearly enable one skilled in the art to make and use the invention, and describes several embodiments, adaptations, variations, alternatives and uses of the invention, including what is presently believed to be the best mode of carrying out the invention. As used in this specification and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly indicates otherwise.

Phosphors of the present invention emit green light over a relatively narrow range of emission wavelengths in response to excitation with, for example, ultraviolet, violet, blue, or short wavelength green light. Their narrow emission may appear more saturated and widen the green vertex of the color gamut compared to commercially available green phosphors.

Phosphors of the present invention have the empirical composition RE_(1−w)A_(w)M_(x)E_(y), where RE may be one or more Rare Earth elements (for example, Eu or Gd), A may be one or more elements selected from the group Mg, Ca, Sr, or Ba, M may be one or more elements selected from the group Al, Ga, B, In, Sc, Lu or Y, E may be one or more elements selected from the group S, Se, O, or Te, w is greater than or equal to zero, or greater than or equal to 0.01, or greater than or equal to 0.05, and less than or equal to about 0.8, 2≤x≤4, and 4≤y≤7. Some minor compositional substitutions may also occur from the use of reaction promoters including but not limited to EuF₃, AlCl₃ or I₂. The phosphors may have the same basic pseudoorthorhombic crystal structure as EuGa₂S₄. The phosphors may comprise a mixture of that pseudoorthorhombic crystal phase and one or more binary chalcogenide crystals phases such as for example an M₂E₃ (e.g., Ga₂S₃) crystal phase or an ME (e.g., GaS) crystal phase.

Phosphors of the present invention may show an improvement over known alkaline earth thiogallate phosphors by providing a narrower emission spectrum than is provided by state of the art thiogallate phosphors. Phosphors of the present invention may show an improvement in brightness over EuM₂E₄ compositions such as, for example, EuAl₂S₄, EuAl₂Se₄, and EuGa₂S₄ disclosed by Thi et al. Materials Science & Engineering B14 (1992), No 4, pp. 393-397, Donohue U.S. Pat. No. 3,801,702 (issued Apr. 2, 1974), and Donohue and Hanlon, Journal of the Electrochemical Society: Solid-State Science and Technology (1974), Vol. 121, No. 1, pp. 137-142. Phosphors of the present invention do not appear to show a significant reduction, if any at all, in luminescence efficiency even when the europium percentage far exceeds the range noted by van Haecke as the maximum, and may include rare earth elements (e.g., europium) at concentrations beyond ranges normally considered as doping.

Phosphors of the present invention may be less hygroscopic and therefore more stable in air than prior art thiogallate and related phosphors.

Phosphors of the present invention may be tuned through a wavelength range based upon application requirements by varying the A, M and E components of the composition.

A number of fluxes/reaction promoters have been investigated, such as for example I₂, AlF₃, AlCl₃, AlBr₃, GaCl₃, GaBr₃, BaF₂, LiCl, CsCl, EuF₃, EuCl₃, EuI₂, and Na₂S. Use of promoters with cations other than those in the targeted final product may in some cases result in the formation of alternative phases, which may not meet the desired properties of the invention.

Phosphors of the present invention may be coated to improve reliability or handling of the materials.

The phosphors of the present invention may be optically coupled with an excitation source in any conventional manner. One of the more common methods is to combine phosphors, such as the green phosphors disclosed here, with a red phosphor and optional blue and/or yellow phosphors. The phosphors may be combined together and then added to an encapsulant, such as silicone, epoxy, or some other polymer, or the phosphors may be combined during their addition to the encapsulant. The phosphor loaded encapsulant may then be placed in the optical path of an excitation source. One common method is to deposit the slurry of phosphor or phosphors into an LED (light emitting diode) package which contains an LED die. The slurry is then cured forming an encapsulated LED package. Other methods include forming the encapsulant into a shape or coating the encapsulant onto a substrate which may already be in a particular shape, or may be subsequently formed into a particular shape. Additionally, the phosphor containing encapsulant may be disposed on or near (e.g., coated on) the in-coupling region of a light guide, or on the out-coupling region of a light guide, such as a light guide intended for use in a display. Alternatively, the phosphor composition may be deposited as a thin film on the LED die or on another substrate and subsequently optically coupled to the light source. The combination of an excitation source and the phosphors of the present invention may be used in general lighting, niche lighting applications, display backlighting, or other lighting applications.

Applicant has prepared and characterized a number of example phosphor samples having the empirical composition RE_(1−w)A_(w)M_(x)E_(y) described above. Preparation and characterization of these examples is described below and summarized in tables below. For some samples one or more crystal phases observed by powder x-ray diffraction are reported in addition to the empirical composition. Emission spectra were measured using a Fluorolog-3 spectrofluorometer with xenon lamp or an Ocean Optics spectrometer used in conjunction with an external blue or violet LED excitation source. Excitation spectra were measured using a Fluorolog-3 spectrofluorometer with xenon lamp. Powder x-ray diffraction spectra were measured using a Rigaku MiniFlex600.

Example Eu_(1−w)Ca_(w)M_(x)S_(y) Phosphors

Example 1. Eu_(0.80)Ca_(0.20)Al_(3.45)Ga_(0.63)S_(7.11) (may be a mixture of Eu_(0.80)Ca_(0.20)Al_(1.69)Ga_(0.31)S₄ and (Al,Ga)₂S₃): Eu₂O₃ (1.084 g, 3.08 mol) and Al powder (0.415 g, 15.41 mol) were mixed using a speed mixer 3 times for 45 seconds at 2000 rpm. The mixed powder was fired at 900° C. for 1 hour under H₂S atmosphere in an alumina boat. The fired precursor cake was hand ground in the glovebox to break it into a powder. 300 mg of EuAl_(2.5)S_(4.75) precursor, 40 mg of Al powder, 15 mg CaS, and 75 mg Ga₂S₃ were hand-ground in a mortar with a pestle. The mixed powder was fired in an alumina cup at 950° C. for 1 hour under H₂S atmosphere.

Example 2. Eu_(0.66)Ca_(0.34)Al_(2.86)Ga_(0.56)S_(6.13) (may be a mixture of Eu_(0.66)Ca_(0.34)Al_(1.67)Ga_(0.33)S₄ and (Al,Ga)₂S₃): Eu₂O₃ (1.084 g, 3.08 mol) and Al powder (0.415 g, 15.41 mol) were mixed using a speed mixer 3 times for 45 seconds at 2000 rpm. The mixed powder was fired at 900° C. for 1 hour under H₂S atmosphere in an alumina boat. The fired precursor cake was hand ground in the glovebox to break it into a powder. 300 mg of EuAl_(2.5)S_(4.75) precursor, 40 mg of Al powder, 30 mg CaS, and 80 mg Ga₂S₃ were hand-ground in a mortar with a pestle. The mixed powder was fired in an alumina cup at 950° C. for 1 hour under H₂S atmosphere.

Example 3. Eu_(0.59)Ca_(0.41)Al_(2.71)Ga_(0.72)S_(6.13) (may be a mixture of Eu_(0.59)Ca_(0.41)Al_(1.58)Ga_(0.42)S₄ and (Al,Ga)₂S₃): Eu₂O₃ (1.084 g, 3.08 mol) and Al powder (0.415 g, 15.41 mol) were mixed using a speed mixer 3 times for 45 seconds at 2000 rpm. The mixed powder was fired at 900° C. for 1 hour under H₂S atmosphere in an alumina boat. The fired precursor cake was hand ground in the glovebox to break it into a powder. 300 mg of EuAl_(2.5)S_(4.75) precursor, 45 mg of Al powder, 40 mg CaS, and 115 mg Ga₂S₃ were hand-ground in a mortar with a pestle. The mixed powder was fired in an alumina cup at 950° C. for 1 hour under H₂S atmosphere.

Example 4. Eu_(0.58)Ca_(0.42)Al_(2.57)Ga_(0.58)S_(5.73) (may be a mixture of Eu_(0.58)Ca_(0.42)Al_(1.63)Ga_(0.37)S₄ and (Al,Ga)₂S₃): Eu₂O₃ (1.084 g, 3.08 mol) and Al powder (0.415 g, 15.41 mol) were mixed using a speed mixer 3 times for 45 seconds at 2000 rpm. The mixed powder was fired at 900° C. for 1 hour under H₂S atmosphere in an alumina boat. The fired precursor cake was hand ground in the glovebox to break it into a powder. 300 mg of EuAl_(2.5)S_(4.75) precursor, 42 mg of Al powder, 42 mg CaS, and 95 mg Ga₂S₃ were hand-ground in a mortar with a pestle. The mixed powder was fired in an alumina cup at 960° C. for 1 hour under H₂S atmosphere.

Example 5. Eu_(0.66)Ca_(0.34)Al_(2.86)Ga_(0.62)S_(6.23) (may be a mixture of Eu_(0.66)Ca_(0.34)Al_(1.64)Ga_(0.36)S₄ and (Al,Ga)₂S₃): Eu₂O₃ (1.084 g, 3.08 mol) and powder (0.415 g, 15.41 mol) were mixed using a speed mixer 3 times for 45 seconds at 2000 rpm. The mixed powder was fired at 900° C. for 1 hour under H₂S atmosphere in an alumina boat. The fired precursor cake was hand ground in the glovebox to break it into a powder. 300 mg of EuAl_(2.5)S_(4.75) precursor, 40 mg of Al powder, 30 mg CaS, and 90 mg Ga₂S₃ were hand-ground in a mortar with a pestle. The mixed powder was fired in an alumina cup at 950° C. for 1 hour under H₂S atmosphere.

Example 6. Eu_(0.66)Ca_(0.34)Al_(2.26)Ga_(0.49)S_(5.11) (may be a mixture of Eu_(0.66)Ca_(0.34)Al_(1.64)Ga_(0.36)S₄ and (Al,Ga)₂S₃): Eu₂O₃ (1.084 g, 3.08 mol) and Al powder (0.415 g, 15.41 mol) were mixed using a speed mixer 3 times for 45 seconds at 2000 rpm. The mixed powder was fired at 900° C. for 1 hour under H₂S atmosphere in an alumina boat. The fired precursor cake was hand ground in the glovebox to break it into a powder. 3 g of EuAl_(2.5)S_(4.75) precursor, 0.2 g of Al powder, 0.3 g CaS, and 0.7 g Ga₂S₃ were hand-ground in a mortar with a pestle. The mixed powder was fired in an alumina cup at 960° C. for 2 hours under H₂S atmosphere.

Example 7. Eu_(0.55)Ca_(0.45)Al_(2.31)Ga_(0.54)S_(5.29) (may be a mixture of Eu_(0.55)Ca_(0.45)Al_(1.62)Ga_(0.38)S₄ and (Al,Ga)₂S₃): Eu₂O₃ (1.084 g, 3.08 mol) and Al powder (0.415 g, 15.41 mol) were mixed using a speed mixer 3 times for 45 seconds at 2000 rpm. The mixed powder was fired at 900° C. for 1 hour under H₂S atmosphere in an alumina boat. The fired precursor cake was hand ground in the glovebox to break it into a powder. 200 mg of EuAl_(2.5)S_(4.75) precursor, 25 mg of Al powder, 32 mg CaS, and 63 mg Ga₂S₃ were hand-ground in a mortar with a pestle. The mixed powder was fired in an alumina cup at 970° C. for 1 hour under H₂S atmosphere.

Example 8. Eu_(0.49)Ca_(0.51)Al_(2.08)Ga_(0.51)S_(4.88) (may be a mixture of Eu_(0.49)Ca_(0.51)Al_(1.61)Ga_(0.39)S₄ and (Al,Ga)₂S₃): Eu₂O₃ (1.084 g, 3.08 mol) and Al powder (0.415 g, 15.41 mol) were mixed using a speed mixer 3 times for 45 seconds at 2000 rpm. The mixed powder was fired at 900° C. for 1 hour under H₂S atmosphere in an alumina boat. The fired precursor cake was hand ground in the glovebox to break it into a powder. 300 mg of EuAl_(2.5)S_(4.75) precursor, 37.5 mg of Al powder, 60 mg CaS, and 97.5 mg Ga₂S₃ were hand-ground in a mortar with a pestle. The mixed powder was fired in an alumina cup at 950° C. for 1 hour under H₂S atmosphere.

FIG. 1 shows emission spectra for examples 1, 2, 3, 5 and 8 and for an internal reference standard, with excitation at 450 nm. FIG. 2 shows excitation spectra for examples 1, 2, 3, 5 and 8, with emission monitored at the emission maximum.

Example 9. Eu_(0.5)Ca_(0.5)Al_(2.25)Ga_(0.75)S_(5.5) (may be a mixture of Eu_(0.5)Ca_(0.5)Al_(1.5)Ga_(0.5)S₄ and (Al,Ga)₂S₃): Pre-made EuAl₂S₄ was combined with CaS, Al, and Ga₂S₃ in the desired stoichiometry. The mixture was heated under flowing H₂S.

Example 10. Eu_(0.5)Ca_(0.5)Al_(2.25)Ga_(0.75)S_(5.5) (may be a mixture of Eu_(0.5)Ca_(0.5)Al_(1.5)Ga_(0.5)S₄ and (Al,Ga)₂S₃): EuS was combined with CaS, Al, and Ga₂S₃ in the desired stoichiometry. The mixture was heated under flowing H₂S.

Example 11. Eu_(0.085)Ca_(0.915)Al_(2.55)Ga_(0.45)S_(5.5) (may be a mixture of Eu_(0.085)Ca_(0.915)Al_(1.7)Ga_(0.3)S₄ and (Al,Ga)₂S₃): EuS was combined with CaS, Al, and Ga₂S₃ in the desired stoichiometry. The mixture was heated under flowing H₂S.

Example 12. Eu_(0.5)Ca_(0.5)Al_(2.25)Ga_(0.75)S_(5.5) (may be a mixture of Eu_(0.5)Ca_(0.5)Al_(1.5)Ga_(0.5)S₄ and (Al,Ga)₂S₃): Pre-made EuAl₂S₄ was combined with CaS, Al, and Ga₂S₃ in the desired stoichiometry, plus 10% CsCl was added as flux. The mixture was heated under flowing H₂S.

Example 13. Eu_(0.7)Ca_(0.3)Al_(2.7)S_(5.05) (may be a mixture of Eu_(0.5)Ca_(0.5)Al₂S₄ and Al₂S₃): 0.542 g Eu, 0.110 g CaS, 1.033 g Al₂S₃, 0.114 g S and 0.090 g AlCl₃ were ground together in a mortar and pestle in an argon filled glovebox. The mixture of reactants was divided equally between four sealed fused silica tubes. The tubes were heated together in a box furnace with the following heating profile: ramp from room temperature to 400° C. over 120 min, dwell at 400° C. for 60 min, ramp from 400° C. to 900° C. over 150 min, dwell at 900° C. for 360 min, then ramp to room temperature over 1080 min.

Example 14. Eu_(0.7)Ca_(0.3)Al_(2.4)Ga_(0.3)S_(5.05) (may be a mixture of Eu_(0.7)Ca_(0.3)Al_(1.78)Ga_(0.22)S₄ and (Al,Ga)₂S₃): 0.523 g Eu, 0.106 g CaS, 0.886 g Al₂S₃, 0.174 g Ga₂S₃, 0.110 g S and 0.090 g AlCl₃ were ground together in a mortar and pestle in an argon filled glovebox. The mixture of reactants was divided equally between four sealed fused silica tubes. The tubes were heated together in a box furnace with the following heating profile: ramp from room temperature to 400° C. over 120 min, dwell at 400° C. for 60 min, ramp from 400° C. to 900° C. over 150 min, dwell at 900° C. for 360 min, then ramp to room temperature over 1080 min.

Example 15. Eu_(0.95)Ca_(0.05)Al₂S₄: CaS, Eu, Al and S were combined in appropriate ratios with a 35% excess of Al and 10 mg excess S in an Ar filled glove box to form approximately 400 mg of reactants and sealed under vacuum in fused silica tubes. The sample was fired twice at 800 ° C. with an intermediate grinding with 10 mg excess S in an Ar filled glove box.

Example 16. Eu_(0.79)Ca_(0.21)Al₂S₄: 400 mg of europium calcium thioaluminate was prepared with 21 mol % Ca from CaS, Eu, Al, and S with a 35% excess of Al and 10 mg excess S. The precursors were mixed with a mortar and pestle in an Ar-filled glovebox then sealed under vacuum in fused silica tubes. The reaction was done at 800° C. for 12 hours with an intermediate step at 400° C.

Example 17. Eu_(0.01)Ca_(0.99)Al₃S_(5.5) (may be a mixture of Eu_(0.01)Ca_(0.99)Al₂S₄ and Al₂S₃): A 400 mg batch of europium calcium thioaluminate with 1 mol % Europium was prepared from CaS, EuF₃, Al, S, and Eu. 200 mg of the precursor mix was reacted under flowing H₂S at 1000° C. for 90 minutes with a boron oxygen getter.

Example 18. Eu_(0.02)Ca_(0.98)Al₃S_(5.5) (may be a mixture of Eu_(0.02)Ca_(0.98)Al₂S₄ and Al₂S₃): A 400 mg batch of europium calcium thioaluminate with 2 mol % Europium was prepared from CaS, EuF₃, Al, S, and Eu. 200 mg of the precursor mix was reacted at 1000° C. under flowing H₂S for 90 minutes with a boron oxygen getter.

Example 19. Eu_(0.05)Ca_(0.95)Al₃S_(5.5) (may be a mixture of Eu_(0.02)Ca_(0.98)Al₃S_(5.5) and Al₂S₃): A 400 mg batch of europium calcium thioaluminate with 5 mol % Europium was prepared from CaS, EuF₃, Al, S, and Eu. 200 mg of the precursor mix was reacted at 1000° C. under flowing H₂S for 90 minutes with a boron oxygen getter.

Example 20. Eu_(0.085)Ca_(0.915)Al₃S_(5.5) (may be a mixture of Eu_(0.085)Ca_(0.915)Al₂S₄ and Al₂S₃): A 400 mg batch of europium calcium thioaluminate with 8.5 mol % Europium was prepared from CaS, EuF₃, Al, S, and Eu. 200 mg of the precursor mix was reacted at 1000° C. under flowing H₂S for 90 minutes with a boron oxygen getter.

Example 21. Eu_(0.01)Ca_(0.88)Al₃S_(5.5) (may be a mixture of Eu_(0.12)Ca_(0.88)Al₂S₄ and Al₂S₃): A 400 mg batch of europium calcium thioaluminate with 12 mol % Europium was prepared from CaS, EuF₃, Al, S, and Eu. 200 mg of the precursor mix was reacted at 1000° C. under flowing H₂S for 90 minutes with a boron oxygen getter.

Example 22. Eu_(0.01)Ca_(0.99)Al₃S_(5.5) (may be a mixture of Eu_(0.01)Ca_(0.99)Al₂S₄ and Al₂S₃): A 400 mg batch of europium calcium thioaluminate was prepared from CaS, EuF₃, Al, and S, with 1 mol % Eu. 1 wt % LiCl was added to the reaction mixture. 200 mg of the precursor mix was reacted at 1000° C. under flowing H₂S for 90 mins with a boron oxygen getter.

Example 23. Eu_(0.02)Ca_(0.98)Al₃S_(5.5) (may be a mixture of Eu_(0.02)Ca_(0.98)Al₂S₄ and Al₂S₃): A 400 mg batch of europium calcium thioaluminate was prepared from CaS, EuF₃, Al, and S, with 2 mol % Eu. 1 wt % LiCl was added to the reaction mixture. 200 mg of the precursor mix was reacted at 1000° C. under flowing H₂S for 90 mins with a boron oxygen getter.

Example 24. Eu_(0.05)Ca_(0.95)Al₃S_(5.5) (may be a mixture of Eu_(0.05)Ca_(0.95)Al₂S₄ and Al₂S₃): A 400 mg batch of europium calcium thioaluminate was prepared from CaS, EuF₃, Al, and S, with 5 mol % Eu. 1 wt % LiCl was added to the reaction mixture. 200 mg of the precursor mix was reacted at 1000° C. under flowing H₂S for 90 mins with a boron oxygen getter.

Example 25. Eu_(0.085)Ca_(0.915)Al₃S_(5.5) (may be a mixture of Eu_(0.085)Ca_(0.915)Al₂S₄ and Al₂S₃): A 400 mg batch of europium calcium thioaluminate was prepared from CaS, EuF₃, Al, and S, with 8.5 mol % Eu. 1 wt % LiCl was added to the reaction mixture. 200 mg of the precursor mix was reacted at 1000° C. under flowing H₂S for 90 mins with a boron oxygen getter.

Example 26. Eu_(0.12)Ca_(0.88)Al₃S_(5.5) (may be a mixture of Eu_(0.12)Ca_(0.88)Al₂S₄ and Al₂S₃): A 400 mg batch of europium calcium thioaluminate was prepared from CaS, EuF₃, Al, and S, with 12 mol % Eu. 1 wt % LiCl was added to the reaction mixture. 200 mg of the precursor mix was reacted at 1000° C. under flowing H₂S for 90 mins with a boron oxygen getter.

Example 27. Eu_(0.12)Ca_(0.88)Al₃S_(5.5) (may be a mixture of Eu_(0.15)Ca_(0.88)Al₂S₄ and Al₂S₃): A 400 mg batch of europium calcium thioaluminate was prepared from CaS, EuF₃, Al, and S, with 15 mol % Eu. 1 wt % LiCl was added to the reaction mixture. 200 mg of the precursor mix was reacted at 1000° C. under flowing H₂S for 90 mins with a boron oxygen getter.

Example 28. Eu_(0.20)Ca_(0.80)Al₃S_(5.5) (may be a mixture of Eu_(0.15)Ca_(0.88)Al₂S₄ and Al₂S₃): A 400 mg batch of europium calcium thioaluminate was prepared from CaS, EuF₃, Al, and S, with 20 mol % Eu. 1 wt % LiCl was added to the reaction mixture. 200 mg of the precursor mix was reacted at 1000° C. under flowing H₂S for 90 mins with a boron oxygen getter.

FIG. 3 shows emission spectra for examples 22-28 and for an internal reference standard, with excitation at 450 nm.

Example 29. Eu_(0.085)Ca_(0.915)Ga₂S₄: CaS, Eu, Ga₂S₃, and S were combined in appropriate ratios with a 35% excess of Al and 10 mg excess S in an Ar filled glove box to form approximately 400 mg of reactants and sealed under vacuum in a fused silica tube. The tube was heated using the following heating profile 290° C. (17 h), 770° C. (24 h), 870° C. (24 h) before cooling to room temperature. The sample was given an intermediate grinding with 10 mg excess S in an Ar filled glove box, sealed under vacuum in a fused silica tube and heated using a second heating profile: 400° C. (6 h), 1000° C. (3 h) before cooling to room temperature. PXRD shows a majority of the desired phase.

Example 30. Eu_(0.085)Ca_(0.915)Ga₂S₄: CaS, Eu, Ga₂S₃, and S were combined in appropriate ratios with a 35% excess of Al and Ga₂S₃ and 10 mg excess S in an Ar filled glove box to form approximately 400 mg of reactants and sealed under vacuum in a fused silica tube. The tube was heated using the following heating profile 290° C. (17 h), 770° C. (24 h), 870° C. (24 h) before cooling to room temperature. The sample was given an intermediate grinding with 10 mg excess S in an Ar filled glove box, sealed under vacuum in a fused silica tube and heated using a second heating profile: 400° C. (6 h), 1000° C. (3 h) before cooling to room temperature. PXRD shows a majority of the desired phase.

Example 31. Eu_(0.085)Ca_(0.915)Al_(0.6)Ga_(1.4)S₄: CaS, Eu, Al, Ga₂S₃, and S were combined in appropriate ratios with a 35% excess of Al and Ga₂S₃ and 10 mg excess S in an Ar filled glove box to form approximately 400 mg of reactants and sealed under vacuum in a fused silica tube. The tube was heated using the following heating profile 290° C. (17 h), 770° C. (24 h), 870° C. (24 h) before cooling to room temperature. The sample was given an intermediate grinding with 10 mg excess S in an Ar filled glove box, sealed under vacuum in a fused silica tube and heated using a second heating profile: 400° C. (6 h), 1000° C. (3 h) before cooling to room temperature. PXRD shows a majority of the desired phase.

Example 32. Eu_(0.085)Ca_(0.915)Al_(0.7)Ga_(1.3)S₄: CaS, Eu, Al, Ga₂S₃, and S were combined in appropriate ratios with a 35% excess of Al and Ga₂S₃ and 10 mg excess S in an Ar filled glove box to form approximately 400 mg of reactants and sealed under vacuum in a fused silica tube. The tube was heated using the following heating profile 290° C. (17 h), 770° C. (24 h), 870° C. (24 h) before cooling to room temperature. The sample was given an intermediate grinding with 10 mg excess S in an Ar filled glove box, sealed under vacuum in a fused silica tube and heated using a second heating profile: 400° C. (6 h), 1000° C. (3 h) before cooling to room temperature. PXRD shows a majority of the desired phase.

Example 33. Eu_(0.085)Ca_(0.915)Al_(0.8)Ga_(1.2)S₄: CaS, Eu, Al, Ga₂S₃, and S were combined in appropriate ratios with a 35% excess of Al and Ga₂S₃ and 10 mg excess S in an Ar filled glove box to form approximately 400 mg of reactants and sealed under vacuum in a fused silica tube. The tube was heated using the following heating profile 290° C. (17 h), 770° C. (24 h), 870° C. (24 h) before cooling to room temperature. The sample was given an intermediate grinding with 10 mg excess S in an Ar filled glove box, sealed under vacuum in a fused silica tube and heated using a second heating profile: 400° C. (6 h), 1000° C. (3 h) before cooling to room temperature. PXRD shows a majority of the desired phase.

Example 34. Eu_(0.085)Ca_(0.915)Al_(0.9)Ga_(1.1)S₄: CaS, Eu, Al, Ga₂S₃, and S were combined in appropriate ratios with a 35% excess of Al and Ga₂S₃ and 10 mg excess S in an Ar filled glove box to form approximately 400 mg of reactants and sealed under vacuum in a fused silica tube. The tube was heated using the following heating profile 290° C. (17 h), 770° C. (24 h), 870° C. (24 h) before cooling to room temperature. The sample was given an intermediate grinding with 10 mg excess S in an Ar filled glove box, sealed under vacuum in a fused silica tube and heated using a second heating profile: 400° C. (6 h), 1000° C. (3 h) before cooling to room temperature. PXRD shows a majority of the desired phase.

Example 35. Eu_(0.085)Ca_(0.915)Al₁Ga₁S₄: CaS, Eu, Al, Ga₂S₃, and S were combined in appropriate ratios with a 35% excess of Al and Ga₂S₃ and 10 mg excess S in an Ar filled glove box to form approximately 400 mg of reactants and sealed under vacuum in a fused silica tube. The tube was heated using the following heating profile 290° C. (17 h), 770° C. (24 h), 870° C. (24 h) before cooling to room temperature. The sample was given an intermediate grinding with 10 mg excess S in an Ar filled glove box, sealed under vacuum in a fused silica tube and heated using a second heating profile: 400° C. (6 h), 1000° C. (3 h) before cooling to room temperature. PXRD shows a majority of the desired phase.

Example 36. Eu_(0.085)Ca_(0.915)Al₁Ga₁S₄: CaS, Eu, Al, Ga₂S₃, and S were combined in appropriate ratios with a 35% excess of Al and Ga₂S₃ and 10 mg excess S in an Ar filled glove box to form approximately 400 mg of reactants and sealed under vacuum in a fused silica tube. The tube was heated using the following heating profile 290° C. (17 h), 770° C. (24 h), 870° C. (24 h) before cooling to room temperature. The sample was given an intermediate grinding with 10 mg excess S in an Ar filled glove box, sealed under vacuum in a fused silica tube and heated using a second heating profile: 400° C. (6 h), 1000° C. (3 h) before cooling to room temperature. PXRD shows a majority of the desired phase.

Example 37. Eu_(0.085)Ca_(0.915)Al₁Ga₁S₄: CaS, Eu, Al, Ga₂S₃, and S were combined in appropriate ratios with a 35% excess of Al and 10 mg excess S in an Ar filled glove box to form approximately 400 mg of reactants and sealed under vacuum in a fused silica tube. The tube was heated using the following heating profile 290° C. (17 h), 770° C. (24 h), 870° C. (24 h) before cooling to room temperature. The sample was given an intermediate grinding with 10 mg excess S in an Ar filled glove box, sealed under vacuum in a fused silica tube and heated using a second heating profile: 400° C. (6 h), 1000° C. (3 h) before cooling to room temperature. PXRD shows a majority of the desired phase.

FIG. 4 shows emission spectra for examples 29-37 with excitation at 395 nm. FIG. 5 shows excitation spectra for examples 29-36 with emission monitored at the emission maximum. FIG. 6A shows X-ray powder diffraction profiles for examples 29-32. FIG. 6B shows X-ray powder diffraction profiles for examples 33-36.

Example 38. Eu_(0.085)Ca_(0.915)Al_(2.64)Ga_(0.36)S_(5.5) (may be a mixture of Eu_(0.085)Ca_(0.915)Al_(1.76)Ga_(0.24)S₄ and (Al,Ga)₂S₃): CaS, Eu, Al, Ga₂S₃ and S were combined in appropriate amounts and reacted under flowing H₂S.

Example 39. Eu_(0.085)Ca_(0.915)Al_(2.64)Ga_(0.36)S_(5.5) (may be a mixture of Eu_(0.085)Ca_(0.915)Al_(1.76)Ga_(0.24)S₄ and (Al,Ga)₂S₃): Identical to example 38, however, used EuS instead of Eu metal as europium source. CaS, EuS, Al, Ga₂S₃ and S were combined in appropriate amounts and reacted under flowing H₂S.

Example 40. Eu_(0.085)Ca_(0.915)Al_(2.64)Ga_(0.36)S_(5.5) (may be a mixture of Eu_(0.085)Ca_(0.915)Al_(1.76)Ga_(0.24)S₄ and (Al,Ga)₂S₃): Identical to example 38, however, used EuF₃ instead of Eu metal as europium source. CaS, EuF₃, Al, Ga₂S₃ and S were combined in appropriate amounts and reacted under flowing H₂S.

Example 41. Eu_(0.085)Ca_(0.915)Al_(2.64)Ga_(0.36)S_(5.5) (may be a mixture of Eu_(0.085)Ca_(0.915)Al_(1.76)Ga_(0.24)S₄ and (Al,Ga)₂S₃): Identical to example 40, however, no elemental sulfur was used in the initial formulation. CaS, EuF₃, Al, and Ga₂S₃ were combined in appropriate amounts and reacted under flowing H₂S.

Example 42. Eu_(0.085)Ca_(0.915)Al_(2.64)Ga_(0.36)S_(5.5) (may be a mixture of Eu_(0.085)Ca_(0.915)Al_(1.76)Ga_(0.24)S₄ and (Al,Ga)₂S₃): Identical to example 40, however, 5% of the CaS was substituted with CaCO₃ in the initial formulation. CaS, CaCO₃, EuF₃, Al, Ga₂S₃, and S were combined in appropriate amounts and reacted under flowing H₂S.

Example 43. Eu_(0.085)Ca_(0.915)Al_(2.64)Ga_(0.36)S_(5.5) (may be a mixture of Eu_(0.085)Ca_(0.915)Al_(1.76)Ga_(0.24)S₄ and (Al,Ga)₂S₃): Identical to example 40, however, 5% of the CaS was substituted with CaF₂ in the initial formulation. CaS, CaF₂, EuF₃, Al, Ga₂S₃, and S were combined in appropriate amounts and reacted under flowing H₂S.

Example 44. Eu_(0.085)Ca_(0.915)Al_(2.64)Ga_(0.36)S_(5.5) (may be a mixture of Eu_(0.085)Ca_(0.915)Al_(1.76)Ga_(0.24)S₄ and (Al,Ga)₂S₃): Identical to example 41, however, used EuS rather than EuF₃ in the initial formulation. CaS, EuS, Al, and Ga₂S₃ were combined in appropriate amounts and reacted under flowing H₂S.

Table 1 below summarizes emission properties of Eu_(1−w)Sr_(w)M_(x)S_(y) phosphor examples 1-44.

For comparison, samples from examples 11 and 12 were left out overnight in air. After overnight exposure to atmospheric moisture, example 11 (50% Eu) was still bright green and emitted brightly under illumination from a violet LED. In contrast, example 12 (8.5% Eu) was much paler and barely emissive.

Example Eu_(1−w)Sr_(w)M_(x)S_(y) Phosphors

Magnesium doped samples were prepared from stoichiometric mixes of Eu, Mg, Al, S, powders and Ga₂S₃ powder, when appropriate, with a 35% excess of Al and Ga₂S₃, when appropriate, and 10 mg excess S which were ground together in an argon filled glovebox and sealed in a quartz tube. The samples were heated in a box furnace to 400° C. for 6 hours then 800 ° C. for 12 hours. XRD showed varying levels of EuAl₂S₄, MgAl₂S₄ and EuS. Each sample showed emission around 500 nm and a shoulder around 450 nm when excited at 395 nm. An excitation scan with emission monitored at 500 nm showed an excitation maximum at about 390 nm, with a gradual decrease in excitation intensity to about 460 nm, followed by a sharp decrease in excitation intensity that decreases below about 30% by 490 nm. The decrease in excitation intensity is more pronounced with increasing Mg content. These results indicate Mg incorporation into the EuAl₂S₄, as well as some Eu doped MgAl₂S₄.

Second firing: Samples were ground again with a mortar and pestle under an argon atmosphere and sealed in a quartz tube. The samples were heated again in a box furnace to 400° C. for 6 hours then 800° C. for 12 hours. Again, XRD showed varying levels of EuAl₂S₄, MgAl₂S₄ and EuS. With 395 nm excitation, only the emission peak ca. 500 nm was observed. There is a slight decrease in peak emission wavelength with the reaction stoichiometry that has Mg present in at least a two-fold excess compared to Eu. The excitation spectra follow a similar trend as noted after the first firing, peaking around 385 nm, and gradually decreasing to about 460 nm, where the extent of excitation intensity decrease is more pronounced with increased Mg content in reaction mixture.

Third firing: Samples were ground again with a mortar and pestle under an argon atmosphere with 10 weight percent sulfur added. The samples were heated to 400° C. for 6 hours then 900° C. for 24 hours. XRD showed varying levels of EuAl₂S₄, and MgAl₂S₄ commensurate with reaction stoichiometry. With 395 nm excitation, only the emission peak ca. 500 nm was observed. There is a slight decrease in peak emission wavelength when the reaction stoichiometry has Mg present in at least a two-fold excess compared to Eu. The excitation spectra show a marked difference, as the excitation maxima which were previously around 385 nm have shifted to approximately 455 nm.

After Second Firing

Example 45. Eu_(0.95)Mg_(0.05)Al₂S₄

Example 46. Eu_(0.86)Mg_(0.14)Al_(1.72)Ga_(0.28)S₄

Example 47. Eu_(0.79)Mg_(0.21)Al₂S₄

Example 48. Eu_(0.65)Mg_(0.35)Al₂S₄

Example 49. Eu_(0.50)Mg_(0.50)Al₂S₄

Example 50. Eu_(0.34)Mg_(0.66)Al₂S₄

Example 51. Eu_(0.10)Mg_(0.90)Al₂S₄

After Third Firing

Example 47. Eu_(0.79)Mg_(0.21)Al₂S₄

Example 48. Eu_(0.65)Mg_(0.35)Al₂S₄

Example 49. Eu_(0.50)Mg_(0.50)Al₂S₄

Example 50. Eu_(0.34)Mg_(0.66)Al₂S₄

Example 51. Eu_(0.10)Mg_(0.90)Al₂S₄

Table 2 below shows the emission properties of examples 45-51 after the second firing. Table 3 below shows the emission properties of examples 47-51 after the third firing.

FIG. 7 shows the X-ray powder diffraction profile for example 47 after the second and third firings. FIG. 8 shows the X-ray powder diffraction profile for example 51 after the second and third firings.

FIG. 9 shows the emission spectra for examples 47-51 after the second firing, with excitation at 395 nm. FIG. 10 shows the excitation spectra for examples 47-51 after the second firing, with emission monitored at 500 nm.

FIG. 11 shows the emission spectra for examples 47-51 after the third firing, with excitation at 395 nm. FIG. 12 shows the excitation spectra for examples 47-51 after the third firing, with emission monitored at 500 nm.

Example Eu_(1−w)Sr_(w)M_(x)S_(y) Phosphors

Strontium doped samples were prepared from stoichiometric mixes of Eu, SrS, Al, and S powders with a 35% excess of Al and 10 mg excess S which were ground together in an argon filled glovebox and sealed in a quartz tube. The samples were heated in a box furnace to 400° C. for 6 hours then 800° C. for 12 hours. Excitation scans with emission monitored at 500 nm showed an excitation maximum at about 380 nm, with a gradual decrease in excitation intensity to about 450 nm, followed by a sharp decrease in excitation intensity that decreases below about 25% by 490 nm. The decrease in excitation intensity towards 450 nm is more pronounced with increasing Sr content.

Example 52. Eu_(0.95)Sr_(0.05) Al₂S₄

Example 53. Eu_(0.79)Sr_(0.21) Al₂S₄

FIG. 13 shows the emission spectra for examples 52 and 53, with excitation at 395 nm. Table 4 below shows the emission properties for examples 52 and 53.

Example Eu_(1−w)Ba_(w)M_(x)S_(y) Phosphors

Barium sulfide was combined with elemental europium, aluminum, and sulfur in appropriate stoichiometric amounts, with a 35% excess of aluminum and a 20% excess of sulfur, forming approximately 400 mg of starting reactant mixture. This mixture was ground with a mortar and pestle and sealed under vacuum in a fused silica tube. The samples were heated to 400° C. over 4 hours, held at temperature for 4 hours, ramped up to 800° C. over 4 hours, held at temperature for 10 hours, then cooled to room temperature over a period of 6 hours. Samples were reground with an additional 10 mg of sulfur under argon, then sealed and heated again under the same profile.

Example 54. Eu_(0.10)Ba_(0.90)Al₂S₄

Example 55. Eu_(0.25)Ba_(0.75)Al₂S₄

Example 56. Eu_(0.40)Ba_(0.60)Al₂S₄

Example 57. Eu_(0.50)Ba_(0.50)Al₂S₄

Example 58. Eu_(0.79)Ba_(0.21)Al₂S₄

Example 59. Eu_(0.95)Ba_(0.05)Al₂S₄

FIG. 14 shows the emission spectra for examples 54 to 57, with excitation at 395 nm. FIG. 15 shows the emission spectrum for example 59, with excitation at 395 nm. FIG. 16 shows the excitation spectra for examples 54 to 57, with emission monitored at 500 nm. Table 5 below shows the emission properties for examples 54-59.

FIG. 17 shows the X-ray powder diffraction profiles for examples 54 to 57 labeled as (a)-(d), respectively, in the figure.

Fabrication of Example Phosphor-Converted LEDs

LED example 1. A phosphor-converted LED was fabricated with phosphor example 12, a red PFS phosphor, and a Plessey 3535 LED package with 450 peak blue. The color point of the emission spectrum is CIE x,y 0.2478, 0.1954. This example is suitable for backlighting applications. The spectral power distribution for this example is shown in FIG. 18.

LED example 2. A phosphor converted LED was fabricated with phosphor example 6, a red PFS phosphor, and a Plessey 3535 LED package with 450 nm peak blue. The color point of the emission spectrum is CIE x,y 0.3446, 0.365. The color temperature is 5062 K, duv is ˜0.0036, and Ra is ˜47. Although this LED would not be suitable for most lighting applications, it illustrates a white color point. The spectral power distribution of this LED is shown in FIG. 19.

LED example 3. A phosphor converted LED was fabricated with phosphor example 6, a red PFS phosphor, and a PowerOpto 457 nm LED (2835 packages). The color point of the emission spectrum is CIE x,y 0.3184, 0.3516. The color temperature is 6102 K, duv is ˜0.0084, and Ra is ˜55.5. The spectral power distribution of this LED is shown in FIG. 20.

LED example 4. A phosphor converted LED was fabricated with phosphor example 7, a BR102Q red phosphor, and a PowerOpto 457 nm LED (2835 package). The color point of the emission spectrum is CIE x,y 0.3517, 0.3134. The color temperature is 4508 K, duv is ˜0.023, and Ra is ˜76. The spectral power distribution of this LED is shown in FIG. 21.

LED example 5. A phosphor converted LED was fabricated with phosphor example 7, a BR102Q red phosphor, and a PowerOpto 457 nm LED (2835 package). The color point of the emission spectrum is CIE x,y 0.4065, 0.3571. 3165 K, duv is ˜0.0156, Ra is ˜81, and R9 is ˜77. The spectral power distribution of this LED is shown in FIG. 22.

LED example 6. A phosphor converted LED was fabricated with phosphor example 4, a BR102Q red phosphor, and a PowerOpto 457 nm LED (2835 package). The color point of the emission spectrum is CIE x,y 0.3298, 0.3620. The color temperature is 5610 K, duv is ˜0.0082, Ra is ˜89, and R9 is ˜70. The spectral power distribution of this LED is shown in FIG. 23.

TABLE 1 Emission properties of Eu_(1-w)Ca_(w)M_(x)S_(y) phosphors. Peak, FWHM, Peak Intensity Relative to Example nm nm an Internal Reference Example 1 518 39.0 80% Example 2 520 39.5 85% Example 3 521 40.5 75% Example 4 522 Example 5 521 43.5 85% Example 6 524 Example 7 524 Example 8 521 43.5 28% Example 9 526 41 94% Example 10 523 42 76% Example 11 521 42 96% Example 12 529 43 106%  Example 13 511 31 Example 14 517 36 Example 15 508 32 Example 16 509 33 Example 17 517 38 48% Example 18 516 39 63% Example 19 517 37 85% Example 20 517 37 100%  Example 21 517 37 97% Example 22 517 39 61% Example 23 517 39 78% Example 24 517 39 94% Example 25 517 38 103%  Example 26 517 37 103%  Example 27 518 38 122%  Example 28 517 37 96% Example 29 556 52 Example 30 550 51 Example 31 546 51 Example 32 546 51 Example 33 546 50 Example 34 543 50 Example 35 541 50 Example 36 528 46 Example 37 518 35 Example 38 521 87% Example 39 521 93% Example 40 521 92% Example 41 518 49% Example 42 521 65% Example 43 519 62% Example 44

TABLE 2 Emission properties of Eu_(1-w)Mg_(w)M_(x)S_(y) phosphors after second firing relative excitation relative intensity at 453 Peak, nm emission nm versus peak Example 2^(nd) firing intensity* excitation Example 45 506 Example 46 508 Example 47 502 100%  95% Example 48 502 98% 92% Example 49 502 93% 91% Example 50 501 74% 88% Example 51 499 58% 83%

TABLE 3 Emission properties of Eu_(1-w)Mg_(w)M_(x)S_(y) phosphors after third firing Example Peak, nm 3^(rd) firing Example 47 506 Example 48 507 Example 49 506 Example 50 504 Example 51 503

TABLE 4 Emission properties of Eu_(1-w)Sr_(w)M_(x)S_(y) phosphors Example Peak FWHM Example 52 507 33 Example 53 503 32

TABLE 5 Emission properties of Eu_(1-w)Ba_(w)M_(x)S_(y) phosphors Example Peak (nm) FWHM (nm) Phases Present in XRD Example 54 482 44 BaAl₂S₄, BaAl₄S₇, EuAl₂S₄ Example 55 491 43 BaAl₂S₄, BaAl₄S₇, EuAl₂S₄ Example 56 497 38 BaAl₄S₇, EuAl₂S₄ Example 57 498 35 BaAl₄S₇, EuAl₂S₄ Example 58 502 33 Example 59 505 32 BaO, EuAl₂S₄

This disclosure is illustrative and not limiting. Further modifications will be apparent to one skilled in the art in light of this disclosure and are intended to fall within the scope of the appended claims. 

What is claimed is:
 1. A light emitting device comprising: a light emitting diode that emits primary light; and a RE_(1−w)A_(w)M_(x)E_(y) phosphor material capable of absorbing at least a portion of the primary light and in response emitting secondary light having a wavelength longer than a wavelength of the primary light; wherein: RE is a Rare Earth element or a mixture of Rare Earth elements; A is selected from the group consisting of Magnesium, Calcium, Strontium, Barium, and mixtures thereof; M is selected from the group consisting of Aluminum, Gallium, Boron, Indium, Scandium, Lutetium, Yttrium, and mixtures thereof; E comprises Sulfur, or Selenium, or Sulfur and Selenium, and optionally Oxygen, Tellurium, or Oxygen and Tellurium; 0.01≤w≤0.8; 2≤x≤4; and 4≤y≤7.
 2. The light emitting device of claim 1, wherein RE is Europium.
 3. The light emitting device of claim 1, wherein 0.30≤w≤0.66.
 4. The light emitting device of claim 1, wherein the RE_(1−w)A_(w)M_(x)E_(y) phosphor has exclusively an EuM₂E₄ pseudoorthorhombic crystal structure.
 5. The light emitting device of claim 1, wherein the RE_(1−w)A_(w)M_(x)E_(y) phosphor has a mixture of predominantly an EuM₂E₄ pseudoorthorhombic crystal structure and one or more binary chalcogenide crystal structures.
 6. The light emitting device of claim 1, wherein the light emitting diode is a laser diode.
 7. The light emitting device of claim 1, wherein the primary light has a wavelength between about 380 nanometers and about 500 nanometers.
 8. The light emitting device of claim 7, wherein the primary light is blue light.
 9. The light emitting device of claim 1, wherein the secondary light has a wavelength between about 475 nanometers and about 560 nanometers.
 10. The light emitting device of claim 1, wherein: RE is Europium; and 0.30≤w≤0.66.
 11. The light emitting device of claim 10, wherein the RE_(1−w)A_(w)M_(x)E_(y) phosphor has exclusively an EuM₂E₄ pseudoorthorhombic crystal structure.
 12. The light emitting device of claim 10, wherein the primary light is blue light.
 13. The light emitting device of claim 1, comprising a second phosphor material capable of absorbing at least a portion of the primary light and in response emitting red light; wherein the combined emission from the light emitting device of unabsorbed primary light, the secondary light, and the red light appears white to a human observer with normal color vision.
 14. The light emitting device of claim 13, wherein: RE is Europium; and 0.30≤w≤0.66.
 15. The light emitting device of claim 14, wherein the RE_(1−w)A_(w)M_(x)E_(y) phosphor has exclusively an EuM₂E₄ pseudoorthorhombic crystal structure.
 16. The light emitting device of claim 14, wherein the primary light is blue light.
 17. The light emitting device of claim 16, wherein the secondary light has a wavelength between about 475 nanometers and about 560 nanometers. 